Nitroalcohol phosphate curing catalyst for aminoplasts



Patented Get. 17, 1950 PATENT OFFICE 3 1 NITROALCOHOL PHOSPHATE CURING 1 cn rALrs'r FOR AMINOPLASTS Herbert J. West, Pittsburgh, Pa., assignor to I acorporationof Maine American Cyanamid Company, New York, N. Y.,

* No Drawing. -'Application November 8, 1946,

" a Serial No. 708,810

This invention relates to aminoplastic-coating compositions having curing accelerators "incorporated therein and more particularly,*it is'directed to nitro aliphatic esters of phosphoric acids incorporated in aminoplastic compositions to accelerate the cure thereof.

Nitro aliphatic estersof phosphoric acids contain two catalyzing nuclei, and'therefore more rap dly accelerate the cure of aminopla'stics.

These esters may be prepared by reacting a phosphoric acid with a nitro derivative of an alcohol capable of forming an' ester therewith. Suitable alcohols 'are the nitro-deriv'ative's of ethanol,

abutanol, 'propanol, and the like? These alcohols, i or a mixture thereof, may be reacted with phosphoric acids and phosphorus "pentoxide, preferably, at subatmosphericltemperatures" in- --the presence of an inert diluent such as benzene,

xylene, and'the like, to" obtainnitro aliphatlc, esters of phosphoric jaci'ds. I

Catalysts prepared inthis manner maybe used to accelerate the curing rate of all types of clear and pigmented coating compositions containing aminoplastic resins; Since aminoplastic resins generally cure to a relatively brittle film, it

- has been found advantageous to blend with the .aminoplastic coating compositions, an alkyd resin which is oil-modified to-efiectcompatability. Likewise, it is preferable to .prepare these coating compositions withan alkylated aminoplastic resin. For example, coating compositons prepared from an alkylated urea or alkylated melamine resin or a mixture thereof, is blended with an oil-modified alkyd resin ,toproduce an efiicient coating composition. I

When a coating composition of the urea-formaldehyde .type is blended'fwith' 0.2+5.0% not a nitro aliphatic polyphosphori'c acid .Jeste'r, tough coating surfaces or films are obtained w thin'tone to two hours at a temperatureof.- 120f 140"E.-F.,

These aminoplastic coating compositions-containing these accelerators have'been found to dry to an insoluble film within 24::hours'at'r00m temperature. The melamine-formaldehyde coating compositions require higher. temperatures for accelerated cure, preferaiblyabove 200 F. These' accelerators are particularly useful in accelerating the cure'of coating -coinpositions 'applied as wood finishes; because low drying temperatures are requiredin this industry. Previously strong mineral acids have been employed for this purpose, but were found to' give: unstable solutions. The solutions containing thes'e'new accelerators arerelatively stable. They. arealso of p'articular value in baked enainel compositions; astheysub- 13 Claims. (01. 260-453) were produced. The addition of "2' cc. of dioxane, -de'stroyed the immiscibility of theliquids an made it a homogeneous solution.

peratures.

stantially reduce the curing timeat elevated tem- The following examples illustrate procedures suitable for the preparation of accelerators ofthe type employed in this invention.

- Example 1 125 parts of Z-nitro-l-butanol were placed in a suitable reaction vessel equipped for mechanical agitation or stirring. Into thisalcohol there was slowly poured, accompanied by vigorous stirring, a slush prepared from 89 parts of phosphorus pentoxide and 130 parts of toluene. The

mixture was vigorously stirred for four hours at v room temperature. Immiscible' layers were ,formed. These layers were separated and the lower layer, saved to be employed as accelerator.

' The. lower layer wasa very dark brown, viscous liquid. 0 g

Suitable accelerators have been prepared wherein the molar equivalent of a nitro alcohol to phosphorus pentoxide has varied from 1:1 to

3:1. Likewise, suitable accelerators are provided 7 employing orthophosphoric acid, metaphosphoric acid and pyrophosphoric acid instead of phosphorus pentoxide. These phosphoric acids and polyphosphoric acids are then reacted with various nitro alcohols such as 2-nitro-2-methylpropanol, and 2-nitro butanol, 2-nitro-1-ethanol, and the like. Any suitable inert diluent such as benzene, toluene, xylene, and the like, may be employed as a reaction medium.

Example 2 A mixture comprising 14.2 parts of phosphorus pentoxde and 62 parts benzene were slowly added to 23.8 parts, of 2.-nitro-2-,-methyl-1 propanol while stirring. The temperature was maintained below 40 0., by occasionally cooling in an ice bath. After several hours of stirring, the solid was completely dissolved, but two liquid phases In the preparation of suitable coating compositions, the following aminoresin dispersions were prepared.

3370 parts of 37% formaldehyde solution were charged to a suitable reaction vessel and neutralized to pH 8.6 with 20% sodium hydroxide,:and

1 there were then addedfi parts of.-85% phosphoric acid. The mixture was heated to C. and 1200 parts of urea were added over a period of an hour. The mixture was thenheatedto f Q.

This resin solution was prepared in the manner described for the preparation of solution A with the exception that approximately 4070 parts of 37% formaldehyde solution were employed with the 1200 parts of urea.

This resin solution was prepared by refluxing approximately 5 mols of formaldehyde and 1 mol of melamine in an acidified mixture of equal parts of butanol and xylene in sufficient quantity to equal the weight of the formaldehyde and melamine. After reaction had been effected, the solution was dehydrated to a desired solid content of 50 Oil modified alkyd res n dispersions were prepared in the following manner:

One mol of phthalc acid, 0.44 mol of soya fatty acids, and 1.06 mols of 100% glycerine were heated to 220 C. and held for a sufficient period of time to control acid number and viscosity, 8 hours usually being sufiicient. This reaction product was diluted with xylene to give a dispersion Containing 55% resin solid.

This resin solution was prepared by heating to 220 C. and holding at this temperature for 4 hours, a mixture of 1.0 mol of phthalic acid, 0.56 mol of soya fatty acids, and 1.0 mol of 100% glycerine. This reacton mxture was diluted with xylene to obtain a dispersion containing 70% resin solids.

One mol of phthalic acid, 0.16 mol castor oil, 0.99 mol of 100% glycerine were heated at 280 C. for 45 minutes followed by a reduction of the temperature to 220 C., at which temperature it was held for three hours. This reaction product was diluted with xylene in sufficient quantity to obtain a dispersion containing 50% resin solids.

One mol of phthalic acid, 0.3 mol of linseed fatty acids, and 1.06 mols of 100% glycerine were heated at 220 C. for three hours. This reaction product was then diluted with xylene in sufficient quantity to obtain a dispersion containing 40% resin solids.

This resin was prepared by effecting the adjunct of 0.6 mol of an alphabeta-unsaturated dicarboxylic acid with 1 mol of a wood or gum rosin by heating to 210-240 C.

The following examples illustrate the coating composition formulations and results obtained by employing accelerators of the type described in this invention.

4 Example 3 To a surfacing composition comprising approximately 6'? parts of resin dispersion A and 33 parts of resin dispersion D, one part of nitro-butyl phosphate was added. This coatin composition was then applied to automotive steel panels and cured for 5 minutes at 250 F. A hard, tough, water-resistant finish was obtained.

Example 4 To a coating composition, prepared by blending approximately 75 parts of resin dispersion A and 25 parts of resin dispersion D, and adjusting said blend with xylene to obtain a dispersion containing 41% resin solids, there was added 1 part of the reaction product obtained by reacting 2 mols of 2-nitro-l-methyl-l-propanol with 1 mol of phosphorus pentoxide. This coating composition or dispersion was flowed onto several pan els of automotive steel immediately after the addit on of the accelerator. The coated steel panels were cured for various periods at various temperatures as follows: 24 hours at 78 F.; and 5 minutes at 250 F. In all cases, tough, clear, hard surfaces were obtained.

Example 5 To a coating composition, prepared by blending approximately '75 parts resin dispersion C and 25 parts of resin dispersion D and diluting the blend with xylene to effect a coating composition containing 42.5% solids, there was added nitrobut-yl ester of pyrophosphoric acid in amounts varying from 1-5 parts. These compositions were applied to automotive steel panels, some of which were heated for 1 hour at 150 F., and others for 10 minutes at 200 F., and the remain der for 5 minutes at 250* F. In all cases, tough, glossy finishes were obtained. Better results were obtained, however, with the compositions containing approxmately 2.5 parts of accelerator per parts resin dispersions when cured at 250 F.

Example 6 To a white enamel, prepared with 50 parts titanium oxide dispersed in a blend of 35 parts of resin dispersion A and 65 parts of resin dispersion D and adiusted with xylene to effect a dispersion containing approximately 55% non-volatile, there was added 1 part of the catalyst prepared by Example 1. This coating composition was sprayed on steel panels, and cured for 5 minutes at 250 F. Tough, hard lustrous, white finishes were obtained.

Example 7 To a white enamel, prepared by dispersing 50 parts titanium oxide in a blend of 25 parts resin dispersion C and 75 parts resin dispersion D and adjusted with xylene to effect a dispersion containing 67 parts non-volatile, there was added 2 parts accelerator prepared by Example 2. Metal panels coated with this composit on and cured for 5 minutes at 250 F. exhibited tough, glossy, hard finishes.

Example 8 50 parts of resin dispersion B, 40 parts of resin dispersion E, 10 parts of resin H, and 1.4 parts of accelerator prepared by Example 2, were blended and the resultin coating composition sprayed onto filled wooden panels. These panels were heated for two'hours at F., removed, and after light sanding, were given another coat, and baked for 2 hours at 125 F. Excellent finishes were obtained which could be rubbed and polished an hour after final baking. These panels had excellent resistance to cycles of heat and cold.

Comparable results have been obtained by blending amino resins dispersion of the type described as A, B, and C with a resin dispersion or dispersions of the type disclosed as D, E, F, and G. Although it is not essential, it is desirable, when preparing a; low temperature baking finish for furniture, to employ a resin of the type disclosed as resin H with a blend of the other resins. The accelerators of the type described herein of nitro aliphatic acid ester of phosphoric acid based on the total weight of resin dispersions and and nitro propyl acid ester of phosphoric acid having only nitro and phosphoric catalytic reactive substituents.

8. A coating composition comprising a dispersion of an alkylated urea-formaldehyde resin, and an oil-modified resin dispersion and 0.2-5.0 parts of nitro aliphatic esters of phosphoric acid, based on 100 parts totalresin dispersion, and havin only nitro and phosphoric catalyticreactive substituents.

containing only nitro and phosphoric catalytic reactive substituents.

2. A coatin composition comprising an alkylated urea-formaldehyde resin dispersion a compatible oil-modified resin dispersion, and a nitro aliphatic ester of phosphoric acid consisting of 0.2+5.0% of the composition and contain-,

ing only nitro and phosphoric catalytic reactive constituents.

3. An aminoplastic coating composition'containing a curing accelerator, said composition comprising a urea-formaldehyde resin, and said accelerator consisting of the nitro butyl acidlester of phosphoric acid having only nitro and-phosphoric catalytic reactive substituents.

4. An amino-plastic coating composition containing a, curing accelerator, said composition comprising a urea-formaldehyde resin, and said curing accelerator consisting of an acid nitro aliphatic ester of phosphoric acid having only nitro and phosphoric catalytic reactive substituents.

5. An amino-plastic coatin composition containing a curing accelerator, said composition comprising a urea-formaldehyde resin and said accelerator consisting of the acid nitro butyl esters of phosphoric acid having only nitro and phosphoric catalytic reactive substituents.

6. An aminoplastic coating composition comprising a thermosetting urea-formaldehyde resin and nitro butyl esters of polyphosphoric acid having only nitro and phosphoric catalytic reactive substituents.

7. An aminoplastic coating composition comprising a thermosetting urea-formaldehyde resin 9. A coating composition comprising an alkylated urea-formaldehyde resin, a compatible alkyd resin and a, curing accelerator consisting of an acid nitro aliphatic ester of phosphoric acid containing only nitro and phosphoric catalytic reactive substituents.

10. A coating composition comprising a thermosetting alkylated urea-formaldehyde resin, a compatible alkyd resin and a curing accelerator consisting of an acid nitro butyl ester of phosphoric acid having only nitro and phosphoric catalytic reactive substituents.

11. A coating composition comprising an alkylated urea-formaldehyde resin, a compatible alkyd resin and acuring accelerator consisting of an acid nitro aliphatic ester of phosphoric acid containing only, nitro and phosphoric catalytic reactive substituents and'said aliphaticradical containing 2 to 4 carbon atoms.

12. A coating composition comprising a thermosetting alkylated urea-formaldehyde resin, a compatible alkyd resin and a nitro aliphatic polyphosphoric acid ester wherein only nitro and phosphoric catalytic reactive substituents exist. 13. A coating composition comprising a thermosetting urea-formaldehyde resin and an acid nitro alkyl ester of phosphoric acid, said ester having phosphoric and nitro catalytic reactive ing 2 to 4 carbon atoms.

substituents only, and said alkyl radical contain- I-IERBERT J. WEST.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES Beilste'ins Handbuchder Organisehen Chemie, 4th ed., vol. I-2nd supplement, page 597, published 1941. 

3. AN AMINOPLASTIC COATING COMPOSITION CONTAINING A CURING ACCELERATOR, SAID COMPOSITION COMPRISING A UREA-FORMALDEHYDE RESIN, AND SAID ACCELERATOR CONSISTING OF THE NITRO BUTYL ACID ESTER OF PHOSPHORIC ACID HAVING ONLY NITRO AND PHOSPHORIC CATALYTIC REACTIVE SUBSTITUENTS. 